The Nitro group in organic sysnthesis - Feuer

						2.1 NITRATION OF HYDROCARBONS 19
	O			-		O
				NO2			(2.50)
	O	Br				O	NO2
		Solvent				Condition	Yield (%)
NaNO2	DMSO					RT, 12 h	35
NaNO2	DMSO-urea					RT, 12 h	36
KNO2	DMSO 18-crown-6					RT, 18 h	37
	DMSO
NaNO2	phloroglucinol					RT, 18 h	51
AgNO2	Et2O					35 °C, 96 h	47
IRA-900-NO−	Benzene					RT, 36 h	82
2
	(CH2)10Br			AgNO2			(CH2)10NO2
N				Et2O, 48 h		N	(2.51)
							58%

Table 2.4 Synthesis of nitro compounds from halides

Halide		Condition	Product		Yield (%)	Ref.
Br	O		O2N	O	63	98
		NaI, acetone
	N Ph	NaNO2, DMSO		N Ph
	OTs	NaI, DMF		NO2	67	99
		NaNO2, DMF
Br O		AgNO2, Et2O	NO2 O		78	100
	Si			Si
	O			O
Me			Me
NC	CO2Et		NC	CO2Et
Me		NaNO2, DMF	Me		58	101
	Me			Me
Br	Et		NO2	Et
		I NaNO2, DMSO		NO2	60	102
	(CH2)6Br	NaNO2, DMSO		(CH2)6NO2	70	103
	OH		OH
I			NO2
O	O	AgNO2, Et2O	O	O	67	104
Si	Si		Si	Si

20 PREPARATION OF NITRO COMPOUNDS

A number of nitro compounds used in natural product synthesis have been prepared by the nitration of alkyl halides. Some recent examples are summarized in Table 2.4.

β-Nitro carbonyl compounds are important for synthesis of natural products. The reaction of alkyl vinyl ketones with sodium nitrite and acetic acid in THF gives the corresponding β-nitro carbonyl compounds in 42–82%.105 This method is better for the preparation of β-nitro carbonyl compounds than the nitration of the corresponding halides.

Schneider and Busch have showed that tetraaza[8.1.8.1]paracyclophane catalyzes the nitration of alkyl bromides with sodium nitrite. In dioxane-water (1:1) at 30 °C, the reaction of 2-bromomethylnaphthalene with sodium nitrite is accelerated by a factor of 20 in the presence of the catalyst.106 Concomitantly, the product ratio of [R-ONO]: [RNO2] changes from 0.50:1 to 0.16:1. Thus, an accumulation of nitrite ions at the positively charged cyclophanes or IRA-900-nitrite form provides a new method for selective nitration of alkyl halides.

2.2 SYNTHESIS OF NITRO COMPOUNDS BY OXIDATION

2.2.1 Oxidation of Amines

The direct oxidation of primary amines into the corresponding nitro derivatives is very useful for fundamental and industrial applications because it provides nitro compounds, which may otherwise be difficult to synthesize by direct nitration methods. Efficient synthetic methods for the conversion of primary amines into the nitro compounds are described in this section. Saturated primary amines undergo oxidation reactions by ozone to give the corresponding nitroalkanes accompanied by several other compounds depending on the reaction conditions.107 This drawback is overcome by ozonation on silica gel. Amines are absorbed on the silica gel by mixing with dry silica gel (dried for 24 h at 450 °C). The silica gel (ca 30 g) containing the amine (0.1–0.2 wt/wt%) was cooled to –78 °C and a stream of 3% of ozone in oxygen passed through it. By this procedure, nitro compounds are obtained in 60–70% yield (Eq. 2.52).108

1-Nitroadamantane is prepared by oxidation of 1-aminoadamantane with peracetic acid and ozone in 95% yield.109

			O3
R		NH2		R		NO2	(2.52)
			silica gel
				60–70%

The use of heterogeneous catalysts in the liquid phase offers several advantages compared with homogeneous counterparts, in that it facilitates ease of recovery and recycling. A chro- mium-containing medium-pore molecular sieve (Si:Cr > 140:1), CrS-2, efficiently catalyzes the direct oxidation of various primary amines to the corresponding nitro compounds using 70% t-butylhydroperoxide (TBHP).110

Aliphatic and aromatic primary amines are rapidly and efficiently oxidized to nitro compounds by dimethyldioxirane.111 Dimethyldioxirane is prepared by reaction of OXONE (DuPont trademark) 2KHSO5-KHSO4-K2SO4 with buffered aqueous acetone.112

In a typical reaction, n-butylamine (0.052 g, 0.7 mmol) in 5 ml of acetone is treated with 95 ml of dimethyldioxirane in acetone solution (0.05 M). The solution is kept at room temperature for 30 min with the exclusion of light (Eq. 2.53). Aromatic amines are converted into nitro compounds by oxidation using OXONE itself.113

	R NH2	O O	R NO2	(2.53)
		acetone
			80–90%

2.2 SYNTHESIS OF NITRO COMPOUNDS BY OXIDATION

21

Oxidation of amines to nitro compounds has been carried out with peracids such as peracetic acid or peroxytrifluoroacetic acid.114 However, the difficulty in handling the hazardous nature of the anhydrous peracids makes these methods less attractive. Gilbert found a general, high-yield synthesis of nitroalkanes from amines using m-chloroperbenzoic acid (m-CPBA) at elevated temperatures.115 A simple synthesis of fully saturated 2-nitrosugar derivatives from the corresponding amino derivatives utilizes an m-CPBA and sodium sulfate reagent system, giving the product in good yields (Eq. 2.54).116

	AcO			AcO
					O
		O	m-CPBA	AcO
	AcO				OAc
		OAc	CHCl3	AcO		(2.54)
	AcO				NO2
		NH2
					85%

Tertiary amines have been oxidized to the corresponding nitro compounds with KMnO4. For example, 2-methyl-2-nitropropane is prepared in 84% yield from t-butylamine with KMnO4

(Eq. 2.55).117 In a similar fashion, 1-aminoadamantane has been oxidized to 1-nitroadamantane in 85% yield with KMnO4 (see Eq. 2.63).118

NH	KMnO4	NO2
2			(2.55)
		83%

Recently, the oxidation of primary aliphatic amines to the corresponding nitro compounds has also been achieved using the catalyst system based on zirconium tetra tert-butoxide and

tert-butyl hydroperoxide in a molecular sieve (50–98% yield) (Eqs. 2.56 and 2.57 and Table 2.5).119

OEt				OEt
		t-BuOOH		O2N
H2N
		Zr(Ot-Bu)		OEt	(2.56)
OEt	4			70%
NH2				NO2
	t-BuOOH
	Zr(Ot-Bu)4				(2.57)
				80%

2.2.2 Oxidation of Oximes

Conversion of carbonyl to nitro groups (retro Nef Reaction) is an important method for the

preparation of nitro compounds. Such conversion is generally effected via oximes using strong oxidants such as CF3CO3H.120

Anhydrous peroxytrifluoroacetic acid is not easy to handle, but the procedure has recently been revised.121 Namely, reaction of urea-hydrogen peroxide complex (UHP) with trifluoroacetic anhydride in acetonitrile at 0 °C gives solutions of peroxytrifluoroacetic acid, which oxidize aldoximes to nitroalkanes in good yields (Eqs. 2.58 and 2.59). Ketoximes fail to react under these conditions, the parent ketone being recovered.

Various convenient methods for the oxidation of oximes to nitro compounds have been developed in recent years. Olah has reported a convenient oxidation of oximes to nitro compounds with sodium perborate in glacial acetic acid (Eq. 2.60).122

22 PREPARATION OF NITRO COMPOUNDS

NOH

NO2

UHP•(CF3CO)2O

O O

(2.58)

O O

CH3CN, 0 ºC, 4 h

75%

NOH

UHP•(CF3CO)2O

NO2

CH3CN, 0 ºC, 5 h

MeO

(2.59)

MeO

(UHP: urea•H2O2)

65%

NOH

NaBO3•4H2O

NO2

(2.60)

AcOH, 55–65 ºC

65%

The conversion of oximes to nitroalkanes has been achieved by employing an Mo(IV) oxodiperoxo complex as oxidant in acetonitrile. Both aldoximes and ketoximes are converted into the corresponding nitroalkanes (Eqs. 2.61 and 2.62),123 representing a complementary synthetic route to the use of the UHP method.

Table 2.5 Conversion of amines to nitro compounds

Amine		Condition	Nitro compound	Yield (%)	Ref
NH2	O	, SiO , –78 °C	NO2	69	108
	3	2
		O O, acetone, RT,		95	111
	30 min
	CrS2, TBHP, MeOH,			85	110
		65 °C, 5 h

NH2

CH2NH2

n-C4H9NH2

t-C4H9NH2

m-CPBA,

75

115

CICH2CH2Cl, 83 °C, 3 h

TBHP, Zr(Ot-Bu)4

m-CPBA, ClCH2CH2Cl, 83 °C, 3 h

O3, SiO2, –78 °C

O O, acetone, RT O3, SiO2, –78 °C CrS2, TBHP

	NO2	82	119
		92	110
		12	108
		97	111
	CH2NO2	66	108
		0	109

CH=NOH

76

O3, SiO2, –78 °C	n-C4H9NO2	65	108
O O, acetone, RT		84	111
m-CPBA,		63	115
ClCH2CH2Cl,
83 °C, 3 h
KMnO4	t-C4H9NO2	83	117
O O, acetone, RT		90	111
O3, SiO2, –78 °C		70	108
TBHP, Zr(Ot-Bu)4		64	119

2.2			SYNTHESIS OF NITRO COMPOUNDS BY OXIDATION 23
NOH			BzOMoO(O ) –							NO2
			2 2								(2.61)
			CH3CN, 40 ºC
				55%
NOH			–							NO2
			BzOMoO(O2)2								(2.62)
			CH3CN, 40 ºC
				92%

Oxidation of oximes to nitro compounds with m-CPBA has been applied to the synthesis of dialkyl 1-nitroalkanephosphonates (Eq. 2.63),124 which are useful reagents for conversion of carbonyl compounds to nitroalkenes.125

OH

NO2 O Oi-Pr

N O

Oi-Pr

m-CPBA

C2H5

CH

P

(2.63)

C2H5

C

P

Oi-Pr

CH2Cl2

65%

Oi-Pr

RT, 72 h

Indirect conversion of oximes to nitro compounds via α-halo nitro compounds has provided a useful method for synthesis of nitro compounds, as shown in Scheme 2.1.

Halogenation of oximes to halonitroso compounds has been achieved by a number of reagents, including chlorine,126 bromine,127 aqueous hypochlorous acid,126, t-butyl hypochlorite,37 and N-bromosuccinimide.128 The resulting halonitroso intermediate is then oxidized to halonitro product with nitric acid,128 ozone,129 aqueous sodium hypochlorite,130 or n-butyl- ammonium hypochlorite.37 The conversion of oximes to α-chloronitro compounds can be carried out by a one-flask operation. For example, 1-chloronitrocyclohexanone is prepared in 98% yield by treatment of cyclohexanone oxime with aqueous hypochlorous acid and by subsequent treatment with a mixture of tetra-n-butylammonium hydrogen sulfate and aqueous sodium hypochlorite. The reductive dechlorination of the α-chloronitro compounds is achieved by catalytic hydrogenolysis with 1 atm H2 over 5% Pd/C in methanol-water (4:1). The final step can be replaced by treatment with either Mg or Zn dust (Eq. 2.64).37

OH

Cl NO2

NO2

N

n-Bu4NHSO4

HClO, pH 5.5

H2/ Pd-C

benzene

NaClO

98%

93%

(2.64) The one-pot conversions of oximes to gem-halonitro compounds have been achieved by using N,N,N,-trihalo-1,3,5-triazines,131 chloroperoxidase in the presence of hydrogen peroxide and potassium chloride,132 or commercial OXONE and sodium chloride.133 Of these methods,

the case of OXONE may be the most convenient (Eq. 2.65).

NOH

OXONE, NaCl

NO2

Cl

CHCl3, 45 ºC, 1 h

(2.65)

83%

O

NOH

Cl

NO

Cl

NO2

H

NO2

R1 R2

R1 R2

R1

R2

R1

R2

R1

R2

Scheme 2.1.

24 PREPARATION OF NITRO COMPOUNDS

Table 2.6 Preparation of polycyclic nitro compounds from oximes

Oxime

Condition

Nitro compound

Yield (%)

Ref.

NOH

1) Br , NaHCO

3

aq

O2N

17

134

2

H

(CF3CO)2O, H2O2

NOH

2) NaBH4

H NO2

1) NBS,

16

141

dioxane/H2O

O2N

O2N

CO2CH3

CO2CH3

2) O3, CH2Cl2

NOH

NO2

NOH

1) Na/NH3, MeOH

H

NO

2) m-CPBA,

2

13

126

NOH

ClCH2CH2Cl

H NO2

OH

HO

N

H2NCONH2,

NO2

N

O2N

Na2HPO4 m-CPBA,

95

30

MeCN, ∆

Energetically rich polynitro compounds have been prepared from polycyclic ketones by the conversion of oximes to nitro compounds, as shown in Table 2.6.

The conversion of oximes to nitro compounds have provided a useful method for the preparation of nitro sugars (see Eqs. 2.66–2.69).36,136,137,138

PhCO2

PhCO2

O

O

(CF3CO)2O, H2O2

HON

CH3CN

O

(2.66)

OO

O2N

O

90%

Ph3CO

O2N

CHO

Ph3CO

O

NO2

OH

NOH

(2.67)

O3, CH2Cl2

O

O

O O

90%

RCO2

RCO2

O

OH OO

1) pyridine, Cr2O7

O

O

(2.68)

2) H

NOH

O

2

3) H2O2, CH3CN

NO2

98%

O

O

O

O

OH

1) pyridine, Cr2O7

NO2

(2.69)

O

2) H2NOH

O

O

3) H2O2, CH3CN

O

O

O

95%

REFERENCES 25

In general, azides are more easily available than nitro compounds by SN2 reaction of the corresponding halides. Thus, the direct conversion of an azide into a nitro group is useful for the synthesis of nitro compounds. Corey and coworkers have reported the easy conversion of azides to nitro compounds via ozonolysis of phosphine imines (Eq. 2.70).139

X

O

O

X = I

NaN3

X = N3

Ph3P

O

DMF

(2.70)

OCH2CCl3

N

O

O

O3

X = NO2

X = N=PPh3

50% (overall)

The standard reaction sequence for transformation of a carboxylic acid into a nitro group is lengthy. Eaton has shortened this conversion via oxidation of isocyanates to nitro compounds with dimethyldioxirane in wet acetone (Eq. 2.71).140

CO2H

1) SOCl2

CON3

2) Me3SiN3

HO2C

N3OC

∆

NCO

O O

NO2

OCN

H2O, acetone

O2N

(2.71)

78%

85%

REFERENCES

1.Olah, G. A., R. Malhotra, and S. C. Narang. Nitration: Methods and Mechanism, VCH, New York, 1989.

2.Schofield, K. Aromatic Nitrations, Cambridge University Press, Cambridge, 1980.

3a. Laszlo, P. Preparative Chemistry Using Supported Reagents, Academic Press, London, 1987. 3b. Smith, K. Solid Supports and Catalysts in Organic Synthesis, Ellis Horwood, Chichester, 1992. 3c. Clark, J. H., and D. J. Macquarrie. Chem. Soc. Rev., 25, 3445 (1996).

4.Olah, G. A., R. Malhotra, and S. C. Narang. J. Org. Chem., 43, 4628 (1978).

5.Harmer, M. A., W. E. Farneth, and Q. Sun. J. Am. Chem. Soc., 118, 7708 (1996).

6.Laszlo, P., and J. Vandormael. Chem. Lett., 1843 (1988).

7.Cornelis, A., A. Gerstmans, and P. Laszlo. Chem. Lett., 1839 (1988).

8.Thomas, R. J., and R. G. Pews. Syn. Commun., 23, 505 (1993).

9.Kwok, T. J., K. Jayasuriya, R. Damavaparu, and B. W. Brodmanj. J. Org. Chem., 59, 4939 (1994).

10.Bekassy, S., T. Cseri, M. Horvath, J. Farkas, and F. Figueras. New. J. Chem., 22, 339 (1998). 11a. Smith, K., A. Musson, and G. A. DeBoos. J. Org. Chem., 63, 8448 (1998).

11b. Smith, K., A. Musson, and G. A. DeBoos. Chem. Commun., 469 (1996).

12a. Waller, F. J., A. G. M. Barrett, D. C. Braddock, and D. Ramprasad. Chem. Commun., 613 (1997). 12b. Waller, F. J., A. G. M. Barrett, D. C. Braddock, R. M. McKinnell, and D. Ramprasad. J. Chem.

Soc., Perkin Trans 1, 867 (1999).

12c. Barrett, A. G. M., D. C. Braddock, R. Ducray, A. M. McKinnell, and F. G. Waller. Synlett., 57 (2000).

13.Waller, F. J., A. C. M. Barrett, D. C. Braddock, and D. Ramprasad. Tetrahedron Lett., 39, 1641 (1998).

14.Ouertani, M., P. Girard, and H. B. Kagan. Tetrahedron Lett, 23, 4315 (1982).

15.Gu, S. X., H. W. Jing, and Y. M. Liang. Synth. Commun., 27, 2793 (1997).

26PREPARATION OF NITRO COMPOUNDS

16.Dove, M. F. A., B. Manz, J. Montogomery, G. Pattenden, and S. A. Wood. J. Chem. Soc., Perkin Trans 1, 1589 (1998).

17.Zhang, W. C., Y. C. Zheng, and Z. T. Huang. Synth. Commun., 27, 3763 (1997).

18.Olah, G. A., P. Ramaiah, G. Sandford, A. Orlinkov, and G. K. S. Prakash. Synthesis, 468 (1994).

19.Fisher, J. W. The Chemistry of Dinitrogen Pentoxide in Nitro Compoundsed. by H. Feuer and A. T. Nielsen, VCH, New York, 1990.

20.Freemantle, M. Chem. Eng. News, 7 (1996).

21.Bakke, J. M., and I. Hegbom. Acta. Chem. Scand., 48, 181 (1994).

22a. Bakke, J. M., and E. Ranes. Synthesis, 281 (1997).

22b. Suzuki, H., M. Iwaya, and T. Mori, Tetrahedron Lett., 38, 5647 (1997).

22c. Bakke, J. M., E. Ranes, and J. Riha. Tetrahedron Lett., 39, 911 (1998). 23. Mori, T., and H. Suzuki. Synlett, 383 (1995).

24a. Suzuki, H., and T. Murashima. J. Chem. Soc., Perkin Trans 1, 903 (1994).

24b. Suzuki, H., T. Murashima, and T. Mori. J. Chem. Soc. Chem. Commun., 1443 (1994).

24c. Suzuki, H., T. Ishibashi, T. Murashima, and K.Tsukamoto. Tetrahedron Lett., 32, 6591 (1991). 24d. Suzuki, H., J. Tomaru, and T. Murashima. J. Chem. Soc. Perkin Trans 1, 2413 (1994).

24e. Suzuki, H., A. Tatsumi , T. Shibasaki, and K. Tsukamoto. J. Chem. Soc. Perkin Trans 1, 339 (1995). 24f. Suzuki, H., T. Takeuchi, and T. Mori. J. Org. Chem., 61, 5944 (1996).

25.Suzuki, H., T. Mori, and K. Maeda. Synthesis, 841 (1994).

26.Enya, T., H. Suzuki, and Y. Hisamatsu. Bull. Chem. Soc. Jpn., 71, 2221 (1998).

27.Suzuki, H., and T. Mori. J. Chem. Soc., Perkin Trans 2, 677 (1996).

28.Njoroge, F. G., B. Vibulbhan, P. Pinto, T. M. Chan, R. Osterman, S. Remiszewski, J. Del Rosario, R. Doll, V. Girijavallabhan, and A. K. Ganguly. J. Org. Chem., 63, 445 (1998).

29.Firouzabadi, H., N. Iranpoor, and M. A. Zolfigol. Synth. Commun., 27, 3301 (1997).

30.Pitts, J. N., K. A. Van Cauwenberghe, D. Grosjean, J. P. Schmid, D. R. Fritz, W. L. Belser, G. B. Kunsdon, and P. M. Hynds. Science, 202, 515 (1978).

31.Tani, K., K. Lukin, and P. E. Eaton. J. Am. Chem. Soc., 1997, 119, 1476.

32.Olah, G. A., and C. H. Lin. J. Am. Chem. Soc., 93, 1259 (1971).

33.Olah, G. A., P. Ramaish, C. B. Rao, G. Sandfold, R. Golam, N. J. Trivedi, and J. A. Olah. J. Am. Chem. Soc., 115, 7246 (1993).

34.Tabushi, I., S. Kojo, and Z. Yoshida. Chem. Lett., 1431 (1971).

35.Suzuki, H., and N. Nonomiya. Chem. Commun., 1783 (1996).

36.Olah, G. A., and C. Rochin. J. Org. Chem., 52, 701 (1987).

37.Corey, E. J., and H. Estreicher. Tetrahedron Lett., 21, 1113 (1980).

38a. Larsen, H. O. In the Chemistry of the Nitro and Nitroso Groups, Part 1, ed. by H. Feuer, Interscience, New York, p. 310 (1969).

38b. von Schickh, O., H. J. Padeken, and A. Segnitz. In Houben-Weyl: Methoden der Organischen Chemie, Vol.10/1 ed. by E. Mulleer, George Thieme Verlag, Stutttgart, 1969, p, 310.

38c. Coomers, R. G. In Comprehensive Organic Chemistry, Vol. 2 ed. by I. O. Sutherland, Pergamon Press, Oxford, p. 326 (1979).

38d. Feuer, H. The Chemistry of Amino, Nitroso and Nitro Compounds and Their Derivatives, Supplemental F; . ed. by S. Patai, John Wiley and Sons; New York, 1982, p. 805–848.

39a. Feuer, H., and J. P. Lawrence. J. Org. Chem., 37, 3662 (1972). 39b. Feuer, H., and H. Friedman. J. Org. Chem., 40, 187 (1975).

40a. Feuer, H., J. W. Shepherd, and C. Savides. J. Am. Chem. Soc., 78, 4364 (1956). 40b. Feuer, H., and R. S. Anderson. J. Am. Chem. Soc., 78, 4364 (1961).

40c. Black, A. P., and F. H. Babers. Org. Synth. 2, 512 (1943).

41.Pfeffer, P.E., and L. S. Silbert. Tetrahedron Lett., 30, 831 (1981).

42.Hauser, F. M., and V. M. Baghdanov. J. Org. Chem., 53, 2872 (1988).

43a. Lukin, K., J. Li, R. Gilardi, and P. E. Eaton. Angew. Chem. Int. Ed. Engl., 35, 864 (1996). 43b. Zang, M. X., P. E. Eaton, and R. Gilardi. Angew. Chem. Int. Ed. Engl., 39, 401 (2000).

44.Haner, R., and D. Seebach. Chimia, 39, 356 (1985).

45.Megges, R., J. Weiland, B. Undeutsch, H. Buchting, and R. Schon. Steroids, 62, 762 (1997).

46.Bull, J. R., E. R. H. Jones, and G. D. Meakins. J. Chem. Soc., 2601 (1965).

47.Pfeiffer, S., B. Mayer, and B. Hemmens. Angew. Chem. Int. Ed. Engl., 38, 3714 (1999). 48a. Ischia, M. Tetrahedron Lett., 37, 5773 (1996).

REFERENCES 27

48b. Kelly, D. R., S. Jones, J. O. Adogun, K. S. V. Koh, D. E. Hibbs, M. B. Hurdthous, and S. K. Jackson . Tetrahedron, 53, 17221 (1997).

48c. Werner, G., J. Kastler, R. Looser, and K. Ballschmiter. Angew. Chem. Int. Ed,. Engl., 38, 1634 (1999). 49a. Larkin, J. M., and K. L. Kreuz. J. Org. Chem., 36, 2574 (1973).

49b. Lachowicz, D. R., and K. L. Kreuz. J. Org. Chem., 32, 3885 (1967).

49c. Stevens, T. E., and W. D. Emmons. J. Am. Chem. Soc., 80, 338 (1958).

49d. Shechter, H., F. Conrad, A. I. L. Daulton, and R. B. Kaplan. J. Am. Chem. Soc., 74, 3052 (1952). 49e. Bordwell, F. G., and E. W. Garbisch, Jr. J. Am. Chem. Soc., 82, 3588 (1960).

50.Borisenko, A. A. A., V. Nikulin, S. Wolfe, N. S. Zefirov, and Z. V. Zyk. J. Am Chem. Soc., 106, 1074 (1984).

51.McMurray, J. E., J. H. Musser, I. Fleming, J. Fortunak and C. Nubling. Org. Synth. Coll. 6, 799 (1988).

52.Seifert, W. K. Org. Synth. Coll. Vol. 6, 837 (1988).

53a. Mukaiyama, T., E. Hata, and T. Yamada. Chem. Lett., 1395 (1995).

53b. Hata, E., T. Yamada, and T. Mukaiyama. Bull. Chem. Soc. Jpn., 68, 3269 (1995).

54. Streekumar, R., R. Padmakumar, and P. Rugmini. Tetrahedron Lett., 39, 2695 (1998). 55a. Valmer, R. S., K. P. Naicker, and P. J. Liesen. Tetrahedron Lett., 39, 3977 (1998). 55b. Campos, P. J., B. Garcia, and M. A. Rodriguez. Tetrahedron Lett., 41, 979 (2000).

56.Hwu, J. R., K. L. Chen, and S. Ananthan. J. Chem. Soc. Chem. Commun., 1425 (1994).

57.Reddy, M. V. R., B. Mehrotra, and Y. D. Vankar. Tetrahedron Lett., 36, 4861 (1995). 58a. Schienbaum, M. L., and M. Dines. J. Org. Chem., 36, 33641 (1971).

58b. Bloom, A. J., M. Fleischman, and J. M. Mellor. J. Chem. Soc., Perkin Trans 1, 2357 (1984).

59.Kunai, A., Y. Yanagi, and K. Sasaki. Tetrahedron Lett., 24, 4443 (1983). 60a. Hassner, A., J. E. Krop, and J. Kent. J. Org. Chem., 34, 2629 (1969).

60b. Szarek, W. A., D. G. Lance, and R. E. Beach. J. Chem. Soc., Chem. Commun., 356 (1968).

61.Sy, W., and A. W. By. Tetrahedron Lett., 26, 1193 (1985).

62.Waldman, S. R., A. P. Monte, A. Bracey, and D. E. Nichols. Tetrahedron Lett., 37, 7889 (1996).

63.Jew, S. S., H. D. Kim, Y. S. Cho, and C. H. Cook. Chem. Lett., 1747 (1986).

64.Ghosh, D., and D. E. Nichols. Synthesis, 195 (1996).

65.Trost, B. M., and T. Shibata. J. Am. Chem. Soc., 104, 3225 (1982).

66a. Hayama, T., S. Tomoda, Y. Takeuchi, and Y. Nomura. Tetrahedron Lett., 23, 4733 (1982). 66b. Hayama, T., S. Tomoda, Y. Takeuchi, and Y. Nomura. J. Org. Chem., 49, 3235 (1984).

67.Backvall, J. E., U. Karlsson, and R. Chinchilla. Tetrahedron Lett., 32, 5697 (1991).

68.Chinchilla, R., and J. E. Backvall. Tetrahedron Lett., 33, 5641 (1992).

69.Najera, C., M. Ysu, U. Karlsson, A. Gogoll, and J. E. Backvall. Tetrahedron Lett., 31, 4199 (1990).

70.Bloom, A. J., and J. Mellor. Tetrahedron Lett., 27, 873 (1986). 71a. Corey, E. J., and H. Estreicher. Tetrahedron Lett., 21, 1113 (1980).

71b. Barrett, A. G. M., M. L. Boys, and T. L. Boehm. J. Org. Chem., 61, 685 (1996). 71c. Chamberlin, A. R., J. E. Stemke, and E. T. Bond. J. Org. Chem., 43, 147 (1978).

72.Einhorn, J., P. Demerseman, and R. Royer. Synthesis, 978 (1984).

73.Patil, G. S., and G. Nagendrappa. Chem. Commun., 1079 (1999).

74.Corey, E. J., and H. Estreicher. J. Am. Chem. Soc., 100, 6294 (1978).

75.Hewlins, S. A., J. A. Murphy, and J. Lin. J. Chem. Soc., Chem. Commun., 559 (1995). 76a. Bloom, A. J., M. Fleischmann, and J. M. Mellor. Tetrahedron Lett., 25, 4971 (1984).

76b. Bloom, A. J., M. Fleischmann, and J. M. Mellor. J. Chem. Soc., Perkin Trans 1, 79 (1986).

77.Jager, V., J. C. Mott, and H. G. Viehe. Chimica, 29, 516 (1975). 78a. Schmitt, R. J., and C. D. Bedford. Synthesis, 132 (1984).

78b. Schmitt, R. J., J. C. Bottaro, R. Malhotra, and C. D. Bedford. J. Org. Chem., 52, 2294 (1987).

79.Fisher, R. H., and H. M. Weitz. Synthesis, 261 (1980).

80a. Ozbal, H., and W. W. Zajac, Jr. J. Org. Chem., 46, 3082 (1981). 80b. Elfehali, F. E., and W. W. Zajac, Jr. J. Org. Chem., 46, 5151 (1981).

81.Feuer, H., and P. M. Pivawer. J. Org. Chem., 31, 3152 (1966).

82.Dampawan, P., and W. W. Zajac, Jr. J. Org. Chem., 47, 1176 (1982).

83.Dampawan, P., and W. W. Zajac, Jr. Synthesis, 545 (1983).

84.Rathore, R., and J. K. Kochi. J. Org. Chem., 61, 627 (1996).

85.Liang, P. Org. Synth., 3, 803 (1955).

28 PREPARATION OF NITRO COMPOUNDS

86a. Reddy, M. V. R., R. Kumareswaran, and Y. D. Vankar. Tetrahedron Lett., 36, 7149 (1995).

86b. Shahi, S.P., A. Gupta, S. V. Pitre, M. V. R. Reddy, R. Kumareswaran, and Y. D. Vankar. J. Org. Chem., 64, 4509 (1999).

87.Stach, H., and M. Hesse. Tetrahedron, 44, 1573 (1988).

88.Ballini, R. Synlett, 1009 (1999).

89a. Ballini, R., and C. Pslestini. Tetrahedron, 35, 5731 (1994).

89b. Dampawan, P., and W. W. Zajac Jr. Tetrahedron Lett., 23, 135 (1982).

90.Ballini, R., and M. Petrini. Synthetic Commun., 16, 1781 (1986).

91.Ballini, R., M. Petrini, and V. Polzonetti. Synthesis, 335 (1992). 92a. Kornblum, N. Org. React., 12, 101 (1962).

92b. Feuer, H., and G. Leston. Org. Synth., Coll. Vol. 4, 368 (1963).

92c. Kornblum, N., and H. E. Ungnade. Org. Synth., Coll. Vol. 4, 724 (1963). 92d. Kornblum, N., and R. K. Blackwood. Org. Synth., Coll. Vol. 4, 454 (1963). 92e. Kornblum, N., and J. W. Powers. J. Org. Chem., 22, 455(1957).

93.Kornblum, N., and W. M. Weaver. J. Am. Chem. Soc., 80, 4333 (1958).

94.Childs, M. E., and W. P. Weber. J. Org. Chem., 41, 3486 (1976).

95.Gelbard, G., and S. Colonna. Synthesis, 113 (1972).

96.Crumbie, R. L., J. S. Nmitz, and H. S. Mosher. J. Org. Chem., 47, 4040 (1982).

97.Wang, C-Y-S., M. Kuramoto, and D. Uemura. Tetrahedron Lett., 37, 1813 (1996).

98.Blake, A. J., E. C. Boyd, R. O. Gould, and R. M. Paton. J. Chem. Soc. Perkin Trans 1, 2841 (1994).

99.Mateos, A. F., G. P. Coca, R. R. Gozalez, and C. T. Herandez. J. Org. Chem., 61, 9097 (1996).

100.Evans, D. A., D. H. B. Ripin, D. Halstead, and K. R. Campos. J. Am. Chem. Soc., 121, 6816 (1999).

101.Grossman, R. B., R. H. Rasne, and B. O. Patrick. J. Org. Chem., 64, 7173 (1999).

102.Fumoto, Y., T. Eguichi, H. Uno, and N. Ono. J. Org. Chem., 64, 6518 (1999).

103.Ballini, R., G. Bisica, and G. Rafaiani. Helv. Chim. Acta, 78, 879 (1995).

104.Sekine, A., N. Kumagai, K. Uotsu, T. Oshima, and M. Shibasaki. Tetrahedron Lett., 41, 509 (2000).

105.Miyakoshi, T., S. Saito, and J. Kumanotani. Chem. Lett., 1677 (1981).

106.Schneider, H. J., and R. Busch. Angew. Chem. Int. Ed. Engl., 23, 911 (1984).

107.Bailey, P. S., and J. E. Keller. J. Org. Chem. 33, 2680 (1968).

108.Keinan, E., and Y. Mazur. J. Org Chem. 42, 844 (1977).

109.Zajac, W. W., Jr., T. R. Walters, and J. M. Woods. J. Org. Chem., 54, 2468 (1989).

110.Jayachandran, B., M. Sasidharan, A. Sudalai, and T. Ravindranathan. J. Chem. Soc., Chem. Commun., 1523 (1995).

111.Murray, R. W., R. Jeyaraman, and L. Mohan. Tetrahedron Lett., 27, 2335 (1986).

112.Murray, R. W., and R. Jeyaraman. J. Org. Chem., 50, 2847 (1985).

113.Zbrowksi, D. L., A. E. Moorman, and K. R. Beck, Jr. Tetrahedron Lett., 29, 4501 (1988).

114.Emmons, W. D. J. Am. Chem. Soc., 79, 5528 (1957).

115.Gilbert, K. E., and W. T. Borden. J. Org. Chem., 44, 659 (1973).

116.Vega-Perez, J. M., J. I. Candela, and F. Iglesias-Guerra. J. Org. Chem., 62, 6606 (1997).

117.Calder, A., A. R Forrester, and S. P. Hepburn. Org. Synth., Coll. Vol. 6, 803 (1988).

118.Stetter, H., and E. Smulders. Chem. Ber., 104, 917 (1971).

119.Krohn, K., and J. Kupke. Eur. J. Org. Chem., 679 (1998).

120.Emmons, W. D., and A. S. Psgano. J. Am. Chem. Soc., 77, 4557 (1955).

121.Ballini, R., E. Marcantoni, and M. Petrini. Tetrahedron Lett., 33, 4835 (1992).

122.Olah, G. A., P. Ramaiah, C. S. Lee, and G. K. S. Prakash. Synlett., 337 (1992).

123.Ballistreri, F. P., E. Barbuzzi, G. A. Tomaselli, and R. M. Toscano. Synlett, 1093 (1996).

124.Zon, J. Synthesis, 661 (1984).

125.Fujii, M. Chem. Lett., 933 (1992).

126.Archibald, T. G., L. C. Garvier, K. Baum, and M. C. Cohen. J. Org. Chem., 54, 2869 (1989).

127.Marchand, A. P., B. E. Arney, Jr., and P. R. Dave. J. Org. Chem., 53, 443 (1988).

128.Iffland, D. C., and G. X. Criner. J. Am. Chem. Soc., 27, 1933 (1962).

129.Barnes, M. W., and J. M. Patterson. J. Org. Chem., 41, 733 (1976).

130.Baum, K., and T. G. Archibald. J. Org. Chem., 53, 4645 (1988).

131.Walters, T. R., W. W. Zajac, Jr., and J. M. Woods. J. Org. Chem., 57, 316 (1992).

132.Zaks, A., A. V. Yabannavar, D. R. Dodds, C. A. Evans, P. R. Das, and R. Malchow. J. Org. Chem., 61, 8692 (1996).